CN110105583B - Metal oxide/ZIF composite material, and preparation method and application thereof - Google Patents
Metal oxide/ZIF composite material, and preparation method and application thereof Download PDFInfo
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- CN110105583B CN110105583B CN201910379247.1A CN201910379247A CN110105583B CN 110105583 B CN110105583 B CN 110105583B CN 201910379247 A CN201910379247 A CN 201910379247A CN 110105583 B CN110105583 B CN 110105583B
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- metal oxide
- zif
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 119
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002135 nanosheet Substances 0.000 claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- 238000002156 mixing Methods 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 108
- 239000000243 solution Substances 0.000 claims description 92
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 73
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000005751 Copper oxide Substances 0.000 claims description 56
- 229910000431 copper oxide Inorganic materials 0.000 claims description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 34
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 34
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 32
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 22
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 imidazole compound Chemical class 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002055 nanoplate Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004146 energy storage Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- QZWWJMGWDBSBQS-UHFFFAOYSA-N 1,5-dichloroimidazole Chemical compound ClC1=CN=CN1Cl QZWWJMGWDBSBQS-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 claims description 3
- NKLOLMQJDLMZRE-UHFFFAOYSA-N 6-chloro-1h-benzimidazole Chemical compound ClC1=CC=C2N=CNC2=C1 NKLOLMQJDLMZRE-UHFFFAOYSA-N 0.000 claims description 3
- DDSBPUYZPWNNGH-UHFFFAOYSA-N 6-n-[(4-nitrophenyl)methyl]-2-n-[[3-(trifluoromethyl)phenyl]methyl]-7h-purine-2,6-diamine Chemical compound C1=CC([N+](=O)[O-])=CC=C1CNC1=NC(NCC=2C=C(C=CC=2)C(F)(F)F)=NC2=C1NC=N2 DDSBPUYZPWNNGH-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000001939 inductive effect Effects 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 60
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 50
- 238000003756 stirring Methods 0.000 description 47
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 45
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 45
- 238000005406 washing Methods 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000001878 scanning electron micrograph Methods 0.000 description 25
- 238000001035 drying Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 230000006698 induction Effects 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- ZULISPCCQYDDNG-UHFFFAOYSA-N zinc methanol dinitrate Chemical compound CO.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] ZULISPCCQYDDNG-UHFFFAOYSA-N 0.000 description 12
- 238000007865 diluting Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013302 MIL-88A Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000013175 zeolitic imidazolate framework-11 Substances 0.000 description 1
- 239000013176 zeolitic imidazolate framework-12 Substances 0.000 description 1
- 239000013166 zeolitic imidazolate framework-65 Substances 0.000 description 1
- 239000013158 zeolitic imidazolate framework-68 Substances 0.000 description 1
- 239000013159 zeolitic imidazolate framework-69 Substances 0.000 description 1
- 239000013160 zeolitic imidazolate framework-70 Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The invention provides a preparation method of a metal oxide/ZIF composite material, which comprises the following steps: s) mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain the metal oxide/ZIF composite material. Compared with the prior art, the preparation method has the advantages that the preparation method takes the two-dimensional inorganic metal oxide nanosheets as the templates for inducing the preparation of the metal oxide/ZIF composite material, the preparation method is simple to operate, complex equipment is not needed, the conditions are mild, the template material is easy to obtain, the process is controllable, the raw material source is wide, the industrialization is favorably realized, and the size of the obtained metal oxide/ZIF composite material is uniform.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to a metal oxide/ZIF composite material, and a preparation method and application thereof.
Background
Metal organic framework Materials (MOFs) are a class of porous crystalline substances with supramolecular structures consisting of metal ions and organic ligands. Due to their ultra-high specific surface area and controllable pore structure, MOFs-derived materials have attracted a great deal of interest in the field of energy conversion and energy storage. To date, a variety of MOFs structures have been converted to amorphous microporous carbon materials via pyrolysis reactions in an inert gas. For example, an article with the number of eaav6009, volume 5 in journal of scientific progress, 2019 reports that the MIL-88A material is used as a precursor to prepare the Ni-doped FeP/C hollow nanorod structure, which shows good electrocatalytic hydrogen production performance.
However, the existing preparation process of the MOFs is uncontrollable, and the directly prepared MOFs has large and uneven size, and is not easy to control, so that the performance of the obtained product is unstable, and the product is not suitable for mass preparation, and a reasonable design is lacking for synthesis of the MOFs. Therefore, how to find a method for controllably synthesizing the MOFs material and the MOFs composite material has become one of the focuses of general attention in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a metal oxide/ZIF composite material, a preparation method and an application thereof, wherein the preparation method is simple and controllable.
The invention provides a preparation method of a metal oxide/ZIF composite material, which comprises the following steps:
s) mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain the metal oxide/ZIF composite material.
Preferably, the metal element in the soluble metal salt is selected from one or more of a group VIII metal element, a group IVB metal element, a group VB metal element, a group VIB metal element, a group VIIB metal element, a group IB metal element and a group IIB metal element;
the soluble metal salt is selected from one or more of soluble metal halide, soluble metal nitrate, soluble metal acetate and soluble metal sulfate;
the organic solvent is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene and N, N-dimethylformamide;
the imidazole compound is selected from one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-nitroimidazole, benzimidazole, 3, 4-dichloroimidazole, purine, 5, 6-dimethylbenzimidazole and 5-chlorobenzimidazole.
Preferably, the metal element in the soluble metal salt is selected from one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, silver, gold, manganese, zinc, cadmium, chromium and mercury; the metal oxide nanosheets are copper oxide nanosheets.
Preferably, the molar ratio of the soluble metal salt to the copper oxide nanosheets is 1: (0.1-40).
Preferably, the step S) is specifically:
s1) mixing the soluble metal salt, the metal oxide nanosheet and the first organic solvent to obtain a first mixed solution; the concentration of the soluble metal salt in the first mixed solution is 0.001-10 mol/L;
mixing the imidazole compound with a second organic solvent to obtain a second mixed solution; the concentration of the imidazole compound in the second mixed solution is 0.001-10 mol/L;
s2) mixing the first mixed solution and the second mixed solution for reaction to obtain the metal oxide/ZI composite material.
Preferably, the thickness of the metal oxide nanosheets is 100nm or less.
Preferably, the metal oxide nanosheets are prepared according to the following steps:
mixing strong acid weak alkaline metal salt, a surfactant and ammonia water to obtain a complex solution;
and mixing the complex solution with a strong alkaline compound for reaction to obtain the metal oxide nanosheet.
Preferably, the strong acid weak base metal salt is selected from one or more of copper sulfate, copper chloride and copper nitrate;
the surfactant is selected from one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and hexadecyl trimethyl ammonium bromide;
the strong alkaline compound is selected from sodium hydroxide and/or potassium hydroxide;
the molar ratio of the strong acid weak alkaline metal salt to the surfactant is (0.001-20): 1;
the molar ratio of the ammonia water to the strong acid weak alkaline metal salt is (0.1-10): 1;
the molar ratio of the strong base to the strong acid and weak base metal salt is (1-10): 1.
the invention also provides the metal oxide/ZIF composite material prepared by the method; the size of the metal oxide/ZIF composite material is less than or equal to 1 mu m.
The invention also provides application of the prepared metal oxide/ZIF composite material in photoelectrocatalysis, electronic devices, energy storage or photoelectric detection.
The invention provides a preparation method of a metal oxide/ZIF composite material, which comprises the following steps: s) mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain the metal oxide/ZIF composite material. Compared with the prior art, the preparation method has the advantages that the preparation method takes the two-dimensional inorganic metal oxide nanosheets as the templates for inducing the preparation of the metal oxide/ZIF composite material, the preparation method is simple to operate, complex equipment is not needed, the conditions are mild, the template material is easy to obtain, the process is controllable, the raw material source is wide, the industrialization is favorably realized, and the size of the obtained metal oxide/ZIF composite material is uniform.
Experiments show that the size of the nano-particles of the metal oxide/ZIF composite material prepared by the invention is less than 500 nm.
Drawings
FIG. 1 is a scanning electron micrograph of copper oxide nanoplates prepared in example 1 of the present invention;
fig. 2 is an X-ray diffraction pattern of copper oxide nanoplates prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 1 of the present invention;
FIG. 4 is a TEM image of the metal oxide/ZIF-8 nanoparticle composite material prepared in example 1 of the present invention;
FIG. 5 is an X-ray diffraction pattern of a metal oxide/ZIF-8 nanoparticle composite material prepared in example 1 of the present invention;
FIG. 6 is a TEM photograph of ZIF-8 nanoparticles prepared in comparative example 1 of the present invention;
FIG. 7 is a SEM photograph of ZIF-8 nanoparticles prepared in comparative example 1 of the present invention;
FIG. 8 is a TEM image of the metal oxide/ZIF-8 nanoparticle composite prepared in example 2 of the present invention;
FIG. 9 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 2 of the present invention;
FIG. 10 is a TEM image of the metal oxide/ZIF-8 nanoparticle composite prepared in example 3 of the present invention;
FIG. 11 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared in example 3 of the present invention;
FIG. 12 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 4 of the present invention;
FIG. 13 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 5 of the present invention;
FIG. 14 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 6 of the present invention;
FIG. 15 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 7 of the present invention;
FIG. 16 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 8 of the present invention;
FIG. 17 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared in example 9 of the present invention;
FIG. 18 is a scanning electron micrograph of a metal oxide/ZIF-8 nanoparticle composite prepared according to example 10 of the present invention;
FIG. 19 is a SEM image of a metal oxide/ZIF-8 nanoparticle composite material prepared in example 11 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a metal oxide/ZIF composite material, which comprises the following steps: s) mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain the metal oxide/ZIF composite material.
The sources of all raw materials in the invention are not particularly limited, and the raw materials can be self-made or commercially available.
The soluble metal salt is preferably one or more of a group VIII metal element, a group IVB metal element, a group VB metal element, a group VIB metal element, a group VIIB metal element, a group IB metal element and a group IIB metal element, more preferably one or more of a group VIII metal element, a group IB metal element and a group IIB metal element, further preferably one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, silver, gold, manganese, zinc, cadmium, chromium and mercury, further preferably one or more of cobalt, iron, nickel, manganese, zinc and cadmium, and most preferably one or more of iron, cobalt and zinc; the soluble metal salt is preferably one or more of soluble metal halide, soluble metal nitrate, soluble metal acetate and soluble metal sulfate, more preferably soluble metal chloride and/or soluble metal nitrate.
The metal oxide nanosheets are preferably copper oxide nanosheets; the thickness of the size of the metal oxide nanosheet is preferably less than or equal to 100nm, more preferably 10-80 nm, still more preferably 30-60 nm, and most preferably 40-50 nm.
The metal oxide nanosheets are preferably prepared according to the following method: mixing strong acid weak alkaline metal salt, a surfactant and ammonia water to obtain a complex solution; and mixing the complex solution with a strong alkaline compound for reaction to obtain the metal oxide nanosheet.
The strong acid and weak alkaline metal salt is preferably one or more of metal sulfate, metal hydrochloride and metal nitrate, more preferably one or more of copper sulfate, copper chloride and copper nitrate; the surfactant is preferably one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and hexadecyl trimethyl ammonium bromide, more preferably polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol or hexadecyl trimethyl ammonium bromide, and further preferably polyvinylpyrrolidone or polyvinyl alcohol; the molar ratio of the strong acid weak alkaline metal salt to the surfactant is preferably (1-2400): 1, more preferably (1 to 1200): 1, and preferably (1-300): 1, most preferably (6-300): 1; the molar ratio of the ammonia water to the strong base weak acid metal salt is preferably (0.1-10): 1, more preferably (0.5 to 8): 1, most preferably (0.5-4): 1.
In the invention, preferably, strong acid alkalescent metal salt and surfactant are mixed in water, and then ammonia water is added for continuous mixing to obtain a complex solution; the mass-to-volume ratio of the strong acid and weak base metal salt to water is preferably 1 g: (50-200) ml, more preferably 1 g: (80-150) ml, more preferably 1 g: 100 ml; after the ammonia water is preferably diluted, adding the ammonia water; the mass concentration of the ammonia water is preferably 25-28%; the dilution multiple is preferably 80-100 times, more preferably 85-95 times, and further preferably 90 times; the method for continuously mixing is preferably stirring and mixing; the time for continuing the mixing is preferably 5min to 12h, more preferably 15min to 6h, still more preferably 15min to 3h, and most preferably 15 to 60 min.
Mixing the complex solution with a strong alkaline compound for reaction; the strongly basic compound is preferably an alkali metal hydroxide, more preferably sodium hydroxide and/or potassium hydroxide; the strongly basic compound is preferably added in the form of an aqueous solution of the strongly basic compound; the concentration of the strong alkaline compound aqueous solution is preferably 0.1-0.5 g/ml, more preferably 0.2-0.4 g/ml, and most preferably 0.2-0.3 g/ml; the molar ratio of the strong basic compound to the strong acid and weak base metal salt is preferably (1-10): 1, more preferably (2-9): 1, more preferably (2-8): 1, most preferably (2-4): 1; in the invention, the strong alkaline compound aqueous solution is preferably slowly dripped into the complex solution for mixing reaction; the mixing reaction is preferably a stirring mixing reaction; the mixing reaction time is preferably 12-120 h, more preferably 30-100 h, and still more preferably 50-80 h.
In order to improve the reaction efficiency and the purity and the availability of the metal oxide nanosheets, after the mixing reaction, post-treatment is preferably carried out to obtain the metal oxide nanosheets; the post-treatment preferably comprises one or more of filtration collection, washing and sonication in that order, most preferably filtration collection, washing and sonication in that order. The specific conditions of the specific process are not particularly limited, and the specific conditions of filtration, collection, washing and ultrasound which are well known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual experimental conditions, raw material conditions and product requirements, wherein the washing is preferably repeated washing, more preferably ethanol washing, and specifically can be ethanol washing for 1-5 times or 2-4 times; the time of the ultrasonic treatment is preferably 1-30 min, more preferably 5-25 min, and most preferably 10-20 min. In order to improve the usability of the metal oxide nanosheet, the metal oxide nanosheet obtained after the post-treatment step can be dispersed in an organic solvent to form a metal oxide nanosheet dispersion liquid; the concentration of the metal oxide nanosheet dispersion is preferably 0.05-10 mg/L, more preferably 0.05-4.5 mg/L, more preferably 0.05-3 mg/L, and most preferably 0.05-2 mg/L; the organic solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene and N, N-dimethylformamide.
The imidazole compound is preferably one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-nitroimidazole, benzimidazole, 3, 4-dichloroimidazole, purine, 5, 6-dimethylbenzimidazole and 5-chlorobenzimidazole.
According to the invention, preferably, the soluble metal salt, the metal oxide nanosheet and the first organic solvent are mixed to obtain a first mixed solution; mixing the imidazole compound with a second organic solvent to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution for reaction to obtain the metal oxide/ZI composite material.
Mixing soluble metal salt, a metal oxide nanosheet and a first organic solvent to obtain a first mixed solution; in order to avoid the phenomenon that the reaction solution has dissolved oxygen in the reaction process of part of soluble metal salt, and the preparation and the appearance of subsequent products are influenced, the reaction can be preferably carried out under the anaerobic condition; preferably, the soluble metal salt and the first organic solvent are mixed, and then the metal oxide nanosheet is added; further, in order to improve the mixing uniformity and the reaction uniformity and stability in the preparation process, the metal oxide nanosheets are preferably added in the form of a metal oxide nanosheet dispersion liquid, so that the dispersibility of the reaction solution is better improved; the metal oxide nanosheet dispersion is as described above and will not be described herein again; the first organic solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene and N, N-dimethylformamide; the concentration of the soluble metal salt in the first mixed solution is preferably 0.001-10 mol/L, more preferably 0.005-5 mol/L, and most preferably 0.01-0.1 mol/L; the molar ratio of the soluble metal salt to the metal oxide nanoplates is preferably 1: (0.1 to 5), more preferably 1: (0.1 to 3), and more preferably 1: (0.1 to 2.5), and more preferably 1: (0.1 to 1), most preferably 1: (0.1 to 0.5); the mixing time is preferably 10-30 min, and more preferably 20-30 min.
Mixing the imidazole compound with a second organic solvent to obtain a second mixed solution; the second organic solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene and N, N-dimethylformamide; the concentration of the imidazole compound in the second mixed solution is preferably 0.001-10 mol/L, more preferably 0.005-5 mol/L, still more preferably 0.01-1 mol/L, and most preferably 0.01-0.1 mol/L.
Mixing the first mixed solution and the second mixed solution for reaction; the mixing reaction time is preferably not less than 1min, more preferably 1min to 48h, still more preferably 1min to 24h, still more preferably 1min to 10 h, still more preferably 5 to 120min, still more preferably 10 to 60min, and most preferably 15 to 30 min.
In order to improve the reaction efficiency, product purity and availability, it is preferable to further include a post-treatment step after the mixing reaction. The present invention is not particularly limited in terms of specific parameters and operations of the post-treatment step, which are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the post-treatment of the present invention includes one or more of filtering collection, washing and drying, more preferably includes one or more of filtering collection, washing and drying in sequence, and most preferably includes filtering collection, washing and drying in sequence. The specific conditions of the above specific processes are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the actual experimental conditions, raw material conditions and product requirements, where the washing is preferably multiple times of washing, more preferably water washing and organic solvent washing, most preferably water washing and alcohol washing, and may be specifically alcohol washing for 1 to 3 times; the drying is preferably room temperature drying, and more preferably room temperature drying for 5-24 h.
The method comprises the steps of preparing ZIF nanoparticles by using a two-dimensional inorganic metal oxide nanomaterial as a template through induction, mixing a copper oxide nanosheet, a soluble metal salt and an organic solvent, and reacting with an imidazole solution to obtain ZIF nanoparticles such as ZIF-8 nanoparticles, ZIF-65 nanoparticles, ZIF-67 nanoparticles, ZIF-68 nanoparticles, ZIF-69 nanoparticles, ZIF-70 nanoparticles, ZIF-11 nanoparticles and ZIF-12 nanoparticles; the preparation method has the advantages of simple operation, no need of complex equipment, mild conditions, easily obtained template materials, controllable process, wide raw material sources and contribution to industrial realization.
Furthermore, the invention takes two-dimensional CuO nano-sheets as template materials, and adopts an epitaxial growth method to obtain ZIF nano-particles which have uniform size and grow on the surface of the copper oxide nano-sheets. In the preparation process, the research on the two-dimensional nanosheet induction effect is helpful for deeply understanding the growth mechanism of the ZIF nanoparticles and guiding the preparation of MOFs derivative materials, and the prepared MOFs derivative materials have very wide application in the fields of photoelectrocatalysis, energy storage, photoelectric detection and the like.
The invention also provides a metal oxide/ZIF composite material prepared by the method; the size of the metal oxide/ZIF composite material is less than or equal to 1 μm, preferably less than or equal to 800nm, more preferably less than or equal to 600nm, and most preferably less than or equal to 500 nm.
The invention also provides application of the metal oxide/ZIF composite material in photoelectrocatalysis, electronic devices, energy storage or photoelectric detection.
In order to further illustrate the present invention, the following will describe in detail a metal oxide/ZIF composite material, a preparation method and applications thereof provided by the present invention with reference to examples.
The reagents used in the following examples are all commercially available; in the embodiment, the used medicines and reagents are purchased from national medicine group chemical reagent company Limited, and the hydrothermal closed reaction vessel is a stainless steel reaction kettle produced by Fujian Shengxin machinery company Limited.
Example 1
1.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
1.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 2mg of copper oxide nanosheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The copper oxide nanosheet obtained in 1.1 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph thereof, as shown in fig. 1.
The copper oxide nanosheet obtained in 1.1 was analyzed by X-ray diffraction to obtain an X-ray diffraction pattern thereof, as shown in fig. 2.
As can be seen from fig. 1 and 2, the copper oxide nanosheets obtained in 1.1 were assembled from nanowires, and the size and thickness of the nanosheets were very uniform.
The metal oxide/ZIF composite material obtained in 1.2 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 3.
The metal oxide/ZIF composite material obtained in 1.2 was analyzed by a transmission electron microscope to obtain a transmission electron micrograph thereof, as shown in fig. 4.
The metal oxide/ZIF composite material obtained in 1.2 was analyzed by X-ray diffraction, and its X-ray diffraction pattern was obtained, as shown in fig. 5.
As can be seen from FIGS. 3 and 4, the prepared ZIF particles are uniformly distributed on the surface of the CuO nanosheet, and the particle size of the particles is 100-200 nm; as can be seen by comparing FIG. 2 with FIG. 5, many peaks appeared before 30 ℃ after the reaction, and these peaks are all peaks of ZIF-8 crystal as can be seen from reference.
Comparative example 1
Preparation of ZIF-8 nanoparticles
Mixing 10mL of 10mmol/L zinc nitrate methanol solution with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the ZIF-8 nanoparticles.
The ZIF-8 nanoparticles obtained in comparative example 1 were analyzed by transmission electron microscopy to obtain a transmission electron micrograph, which is shown in FIG. 6.
The ZIF-8 nanoparticles obtained in comparative example 1 were analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 7.
As can be seen from FIGS. 6 and 7, the particle diameter of the obtained nano-sheet ZIF-8 nano-particle is 200-500 nm.
Example 2
2.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
2.2 preparation of metallic oxide/ZIF-8 nanoparticle composite material by copper oxide nanosheet induction
Dispersing 4mg of copper oxide nanosheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 2 was analyzed by a transmission electron microscope to obtain a transmission electron micrograph, which is shown in fig. 8.
The metal oxide/ZIF composite material obtained in example 2 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 9.
As can be seen from fig. 8 and 9, the prepared ZIF particles are uniformly distributed on the surface of the CuO nanosheet, and the particle size is less than 100 nm. Compared with the metal oxide/ZIF-8 nanoparticle composite material prepared in the embodiment 1, the particles distributed on the CuO nanosheets are sparser.
Example 3
3.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
3.2 preparation of metallic oxide/ZIF-8 nanoparticle composite material by copper oxide nanosheet induction
Dispersing 8mg of copper oxide nanosheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 3 was analyzed by a transmission electron microscope to obtain a transmission electron micrograph, which is shown in fig. 10.
The metal oxide/ZIF composite material obtained in example 3 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 11.
As can be seen from fig. 10 and 11, the prepared ZIF particles are uniformly distributed on the surface of the CuO nanosheet, the particle size of the particles is less than 100nm, and the particle size of some particles is even less than 50 nm. Compared with the metal oxide/ZIF-8 nanoparticle composite material prepared in the embodiment 2, the particles distributed on the CuO nanosheet are more sparse.
Example 4
4.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
4.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nanosheets in 10mL of 2mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 2-methylimidazole methanol solution with the concentration of 2mmol/L, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 4 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 12. As can be seen from fig. 12, the surface of CuO nanoplate has almost no ZIF-8 nanoparticles.
Example 5
5.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
5.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nanosheets in 10mL of 4mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 4 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 5 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, as shown in fig. 13. As can be seen from fig. 13, the surface of CuO nanosheets has almost no ZIF-8 nanoparticles, and the particle size of the ZIF-8 nanoparticles obtained in this example is larger than that of the product of example 4.
Example 6
6.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
6.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nanosheets in 10mL of 8mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 8 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 6 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, as shown in fig. 14. As can be seen from fig. 14, more ZIF-8 nanoparticles appeared on the surface of CuO nanoplates relative to the product of example 5.
Example 7
7.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 12g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
7.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nanosheets in 10mL of 15mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 15 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 7 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, as shown in fig. 15. As can be seen from fig. 15, the surface of CuO nanosheets was almost coated with ZIF-8 nanoparticles.
Example 8
8.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of blue vitriod, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the dissolved blue vitriod, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
8.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nano-sheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6 h.
The metal oxide/ZIF composite material obtained in example 8 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 16. As can be seen from fig. 16, the ZIF-8 nanoparticles appeared on the surface of the CuO nanoplate, but many nanoparticles did not grow on the surface of the CuO nanoplate, relative to the product of example 1.
Example 9
9.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 1.5g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the diluted ammonia water after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
9.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nano-sheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6 h.
The metal oxide/ZIF composite material obtained in example 9 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 17. As can be seen from FIG. 17, the particle size of ZIF-8 nanoparticles on the surface of CuO nanoplates is smaller, about 20 to 50nm, relative to the product of example 1.
Example 10
10.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 6g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
10.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nanosheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 10 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 18. As can be seen from FIG. 18, the particle size of the ZIF-8 nanoparticles on the surface of the CuO nanosheet is about 20-50 nm, and the surface of the CuO is completely coated with the nanoparticles.
Example 11
11.1 Synthesis of copper oxide nanosheets
Weighing 3.0g of copper sulfate pentahydrate and 48g of polyvinylpyrrolidone, dissolving in 300mL of water, diluting 0.93mL of ammonia water (mass fraction is 25-28%) to 90mL of water, mixing the diluted ammonia water with the copper sulfate and the polyvinylpyrrolidone after the copper sulfate and the polyvinylpyrrolidone are dissolved, and stirring for 15min to obtain a mixed solution; dissolving 2.4g of sodium hydroxide in 10mL of water to form a sodium hydroxide solution, slowly and dropwise adding the sodium hydroxide solution into the mixed solution, continuously stirring the reaction solution for 3 days, centrifugally washing the reaction solution once, and drying the reaction solution at room temperature in vacuum to obtain the copper oxide nanosheet.
11.2 preparation of metal oxide/ZIF-8 nanoparticle composite material by induction of copper oxide nanosheet
Dispersing 4mg of copper oxide nanosheets in 10mL of 10mmol/L zinc nitrate methanol solution, stirring for 20min, mixing with 10mL of 10 mmol/L2-methylimidazole methanol solution, fully stirring for 15min, washing with ethanol for three times, and vacuum-drying at room temperature for 6h to obtain the metal oxide/ZIF composite material.
The metal oxide/ZIF composite material obtained in example 11 was analyzed by a scanning electron microscope to obtain a scanning electron micrograph, which is shown in fig. 19. As can be seen from fig. 12, the surface of CuO was completely coated with nanoparticles and some nanoparticles did not grow on the surface of CuO, relative to the product of example 1.
Claims (7)
1. A preparation method of a metal oxide/ZIF composite material is characterized by comprising the following steps:
s) mixing and reacting soluble metal salt, metal oxide nanosheets and imidazole compounds in an organic solvent to obtain a metal oxide/ZIF composite material;
the soluble metal salt is selected from one or more of soluble metal halide, soluble metal nitrate, soluble metal acetate and soluble metal sulfate;
the organic solvent is selected from one or more of methanol, ethanol, propanol, butanol, pentanol, benzene, phenol, toluene and N, N-dimethylformamide;
the imidazole compound is selected from one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-nitroimidazole, benzimidazole, 3, 4-dichloroimidazole, purine, 5, 6-dimethylbenzimidazole and 5-chlorobenzimidazole;
the metal element in the soluble metal salt is selected from one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, copper, silver, gold, manganese, zinc, cadmium, chromium and mercury; the metal oxide nanosheets are copper oxide nanosheets;
the metal oxide nanosheet is prepared according to the following steps:
mixing strong acid weak alkaline metal salt, a surfactant and ammonia water to obtain a complex solution;
mixing the complex solution with a strong alkaline compound for reaction to obtain a metal oxide nanosheet;
the strong acid weak alkaline metal salt is selected from one or more of copper sulfate, copper chloride and copper nitrate;
the surfactant is selected from one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol and hexadecyl trimethyl ammonium bromide;
the molar ratio of the strong acid weak alkaline metal salt to the surfactant is (0.001-20): 1.
2. the production method according to claim 1, wherein the molar ratio of the soluble metal salt to the copper oxide nanoplates is 1: (0.1-40).
3. The preparation method according to claim 1, wherein the step S) is specifically:
s1) mixing the soluble metal salt, the metal oxide nanosheet and the first organic solvent to obtain a first mixed solution; the concentration of the soluble metal salt in the first mixed solution is 0.001-10 mol/L;
mixing the imidazole compound with a second organic solvent to obtain a second mixed solution; the concentration of the imidazole compound in the second mixed solution is 0.001-10 mol/L;
s2) mixing the first mixed solution and the second mixed solution for reaction to obtain the metal oxide/ZIF composite material.
4. The production method according to claim 1, wherein the thickness of the metal oxide nanosheet is 100nm or less.
5. The production method according to claim 1,
the strong alkaline compound is selected from sodium hydroxide and/or potassium hydroxide;
the molar ratio of the ammonia water to the strong acid weak alkaline metal salt is (0.1-10): 1;
the molar ratio of the strong base to the strong acid and weak base metal salt is (1-10): 1.
6. the metal oxide/ZIF composite prepared according to any one of claims 1 to 5, wherein the size of the metal oxide/ZIF composite is 1 μm or less.
7. The use of the metal oxide/ZIF composite prepared according to any one of claims 1 to 5 in photoelectrocatalysis, electronic devices, energy storage or photodetection.
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